Method for producing substantially dry water-insoluble polymers for improved flocculation in the bayer process

ABSTRACT

The present invention is a method of producing substantially dry water insoluble polymers from poly alkyl esters of vinylic monomers for use in a method for the clarification of red mud-containing liquors generated in the Bayer process for the recovery of alumina from bauxite ore. The polymers can be either homopolymers, copolymers or terpolymers. Preferably, the dried emulsion polymers are high molecular weight polymers of poly(methyl acrylate), poly(methyl acrylate/acrylic acid), poly(vinyl acetate/acrylic acid/methyl acrylate), poly(t-butyl methacrylate/acrylic acid/methyl acrylate) and poly(t-butyl acrylate/acrylic acid/methyl acrylate).

FIELD OF THE INVENTION

The present invention is directed to a process for producingsubstantially dry water insoluble polymers from poly alkyl esters ofvinylic monomers for improved flocculation of red mud in the Bayerprocess and for a process of clarification of the red mud-containingliquors generated in the Bayer process for the recovery of alumina frombauxite ore with high molecular weight emulsion polymers.

BACKGROUND OF THE INVENTION

The Bayer process for the production of alumina includes the basic stepsof pulverizing a bauxite ore which is slurried in water and digestedwith caustic at elevated temperatures and pressures. The causticsolution dissolves oxides of aluminum to form an aqueous sodiumaluminate solution that must be separated from the caustic-insolubles ofbauxite ore (red mud). Separation typically occurs through the processof sedimentation and filtration, which are often aided by a flocculant.Once separated, alumina trihydrate can be precipitated out of theaqueous sodium aluminate solution and collected as product.

Specifically, the pulverized bauxite ore is fed into a slurry mixerwhere the slurry makeup water is typically spent liquor and addedcaustic. The bauxite ore slurry is then diluted and passed through adigester under high pressure and temperature conditions where about 98%of the total available alumina is released from the ore ascaustic-soluble sodium aluminate. After digestion, the slurry passesthrough several flash tanks where the pressure of the digested slurry isreduced from several atmospheres to one atmosphere and the temperatureof the slurry is reduced from about 200° C. to about 105° C.

The aluminate liquor leaving the flashing operation contains about 1 to20 weight percent solids. The coarser solids may be removed from thealuminate liquor with “sand trap” cyclones. The finer solids aregenerally separated from the liquor first by settling aided by aflocculant and then filtration. The aluminate liquor slurry leaving theflash tank is diluted by a stream of recycled washer overflow liquor.Any Bayer process slurry taken from the digesters through a subsequentdilution of the slurry, including the flash tanks, but before theprimary settler, is the primary settler feed.

Normally, the primary settler feed is fed to the primary settler whereit is treated with a flocculant. As the mud settles, the clarifiedsodium aluminate solution (“green” or “pregnant” liquor) overflows to aweir and is collected. This overflow from the primary settling tank isthen passed through subsequent process steps.

The clarity of the primary settler overflow is crucial to efficientprocessing of alumina trihydrate because further steps will be requiredif the overflow has not been properly clarified. An overflow liquorcontaining a concentration of suspended solids of about 10-500 mgsuspended solids per liter is typically unacceptable and will requirefurther processing in a secondary clarification stage to achieve thedesired 10 mg suspended solids per liter.

A flocculant is often added to aid in the partial separation of the redmud solids from the pregnant liquor in the primary settler stage.Flocculating agents, such as inverse emulsion liquid polymers, drypolymers and polysaccharides including starch, improve the separation ofinsolubles. Flocculants are able to increase the rate at which solidssettle by reducing the amount of residual solids suspended in the liquorand by decreasing the amount of liquor in the settled solids phase.

Flocculants are highly important in the primary settling stages. Redmuds are comprised of iron oxides (about 50 weight percent), togetherwith silicon oxides, calcium oxides, sodium alumino-silicates, titaniumoxides and other material commonly comprise about 5 to about 50 weightpercent of the bauxite ore. Generally, the muds are comprised of veryfine particles, which hinder separation of red mud particles from thesolubilized alumina liquor. If the rate of separation is too slow,output is diminished and the overall process efficiency is impaired. Ifthe separation is not clean, a more extensive treatment to removeresidual solids will be required.

Conventional treatments include the application of polysaccharides, suchas starch and dextran. For instance, U.S. Pat. No. 3,085,853 to Lesinskiet al. uses native dextrans to increase the rate of sedimentation offinely divided solids in aqueous suspensions. After polysaccharides wereintroduced, synthetic polymeric flocculants were developed which havebecame more popular for use in the Bayer process. Additional polymersinclude those formed from the polymerization of vinyl amine or vinylformamide as disclosed in U.S. Pat. No. 5,346,628; phosphonic acidpolymers as disclosed in U.S. Pat. No. 5,534,235; and polymerscontaining hydroxamic acid groups in U.S. Pat. No. 4,767,540.

Other Bayer process treatments include the combination ofpolysaccharides with synthetic polymeric flocculants. For example, U.S.Pat. No. 3,397,953 to Galvin et al. discloses that polyacrylic acidalone is not suitable as a flocculating agent, instead it teaches theuse of a blend of starch and polyacrylic acid on red mud suspensions.The polyacrylic acids generally have molecular weights of less than300,000. The flocculation and sedimentation activity of the blend isused in the primary settler stage of a bauxite process, and contains atleast about 80 weight percent of the acrylic acid mer with a molecularweight in excess of 50,000 and preferably in excess of 100,000. Otherstarch/polymer combinations are disclosed in U.S. Pat. Nos. 3,397,953;3,541,009; 3,681,012; and 5,008,089.

Emulsions of polymers formed of lower primary alkyl acrylate monomersfor refining alumina are disclosed in U.S. Pat. No. 3,755,531. Moreover,unexamined Japanese Pat. No. 4986-1979 discloses a process for producingan ultra high molecular weight acrylic acid copolymer salt. However,only lower molecular weight polymers which are less effectiveflocculants than higher weight polymers are disclosed in the JapanesePatent.

Disclosed in U.S. Pat. No. 5,286,391 is a process for improving theflocculation of suspended red mud solids in a Bayer process liquorcomprising a water-continuous dispersion containing a polymer dispersedin the water of the continuous phase, wherein the polymer comprises atleast 50 mole percent of mer units having pendant groups that hydrolyzeto pendant carboxylic acid groups. However, this reference suggests thatbecause the in-situ hydrolysis occurs over time and results incontinuous activation, that the optimal polymer would be one containing100 mole percent of mer units having pendant hydrolyzable groups. Bycontrast, this invention discloses that there is an optimal degree ofhydrolysis (not 100%), that occurs in the range of 70-80%.

Oil continuous liquid flocculants (hereafter termed o/c flocculants) andpowder flocculants are typically referred to as synthetic flocculants.Such flocculating agents are added to the primary settler, the mudwashing circuit, mud-dewatering systems including centrifuges and vacuumfilters and to enhance mud stacking in mud disposal sites.

High molecular weight synthetic polymers are often used in conjunctionwith starches. Starch is said to improve supernatant liquor clarity, theinterface between the settled mud and the cleaner supernatant liquor,and reportedly helps to maintain the stability of the settled mud insettlers and washers. However, starch occasionally produces a red mudwhich has poor rheology and undesirable underflow characteristics. Ifnot diluted, the underflow can occasionally become difficult to pump.

The oil continuous flocculants must be inverted prior to application totransfer the flocculant to the water phase of the emulsion. If o/cflocculants are added neat (non-inverted) the polymer flocculant willnot disperse in the Bayer liquor, the oil phase containing theflocculant will plug the injection equipment, and poor activity will beencountered.

Oil continuous liquid flocculants of sodium or ammonium acrylate arelargely used in the bauxite industry for settling the red mud. Since theoil continuous liquid flocculants contain about 25-30% of paraffinicoils as the carrier, one drawback to these flocculants is the liquorfrom which the alumina separates out becomes enriched with increasingamounts of organic material. Since organics in the liquor inhibit theprecipitation of alumina, a flocculant containing the least amount oforganic material is the most desirable. The liquid flocculants aregenerally easier to transfer, store and apply to the process than drypowders. However, shipping costs for the liquids tend to be considerablyhigher since the emulsions contain only about 25-40% polymer solids.Furthermore, some o/c liquids can become unstable if exposed totemperatures below their freezing point.

Dry polymers are an effective alternative to liquid polymers in theflocculation of Bayer process liquors. As opposed to emulsion polymers,dry polymers contribute little to the organic load of the Bayer liquorand are less expensive to ship. While such advantages have made the useof dry polymers more common, they remain under used because of thespecial handling required to ensure the polymers remain dry before use.Dry polymers are extremely hygroscopic and must be handled, stored andprepared without exposing the polymer to moisture or humid air. Once adry polymer has been exposed to moisture or humidity, severe systemplugging and loss of activity will result. The hydration of a drypolymer prior to its use results in product loss, disposal problems, andincreased maintenance costs. Dry polymer storage, solution make-up andfeeding equipment must be very elaborate to prevent hydration.

Additionally, dry polymers are difficult to dissolve in water, with90%+polymer hydration requiring mixing and aging time as high as 2hours. This slow dissolution rate requires large inventories ofsolutions divided into 2 separate tanks. The first tank is the highmixing energy tank where dissolution occurs. The second tank is theworking solution tank from which the polymer solution is drawn and fedinto the process.

Accordingly, it would be advantageous to provide a substantially dryflocculating agent which would expedite the separation of the red mudsolids from the pregnant liquor, improve the clarity of liquor overflow,be easy to handle and feed into the process without the hygroscopiccharacteristics of current dry polymers.

SUMMARY OF THE INVENTION

The present invention is directed to a method for producingsubstantially dry water insoluble polymers from poly alkyl esters ofvinylic monomers for use in a method for the clarification of redmud-containing liquors generated in the Bayer process for the recoveryof alumina from bauxite ore. The polymers can be either homopolymers,copolymers or terpolymers. Preferably, the dried emulsion polymers arehigh molecular weight polymers of poly(methyl acrylate), poly(methylacrylate/acrylic acid), poly(vinyl acetate/acrylic acid/methylacrylate), poly(t-butyl methacrylate/acrylic acid/methyl acrylate) andpoly(t-butyl acrylate/acrylic acid/methyl acrylate).

One aspect of this invention is a process for producing substantiallydry water insoluble high molecular weight polymers from poly alkylesters of vinylic monomers comprising:

spray-drying into a gas stream an aqueous dispersion of a high molecularweight water-continuous emulsion polymer including an emulsifier, asurfactant, water and having an intrinsic viscosity in 2N NaNO₃ at 30°C. of at least 15 dL/g; and

collecting the resultant polymer particles.

A second aspect of the present invention includes a process forproducing substantially dry water insoluble high molecular weightpolymers from poly alkyl esters of vinylic monomers comprising:

drying an aqueous dispersion of a high molecular weight water-continuousemulsion polymer including an emulsifier, a surfactant, water and havingan intrinsic viscosity in 2N NaNO₃ at 30° C. of at least 15 dL/g;

forming a film comprised of the dried aqueous dispersion substantiallyfree of water; and

grinding the film to form a powder of substantially dry polymerparticles.

An additional aspect of this invention is a method of treating Bayerprocess red mud containing liquor comprising the steps of:

adding to the red mud containing liquor a substantially dry waterinsoluble high molecular weight polymer formed from a polymer emulsionof poly alkyl esters of vinylic monomers having an intrinsic viscosityin 2N NaNO₃ at 30° C. of at least 18 dL/g;

forming a red mud phase and a clarified liquor phase; and

recovering the clarified liquor phase.

Another aspect of this invention is a method for treating Bayer processred mud containing liquor comprising the steps of:

adding to the red mud containing liquor an effective amount of asubstantially dry water insoluble high molecular weight polymer formedfrom a homopolymer emulsion wherein the homopolymer has an intrinsicviscosity in 2N NaNO₃ at 30° C. of at least 15 dL/g;

forming a red mud phase and a clarified liquor phase; and

recovering the clarified liquor phase.

A further aspect of this invention is a method for treating Bayerprocess red mud containing liquor comprising the steps of:

adding to the red-mud containing liquor an effective clarifying amountof a substantially dry water insoluble high molecular weight polymerformed from a terpolymer emulsion wherein the terpolymer has anintrinsic viscosity in 2N NaNO₃ at 30° C. of at least 15 dL/g;

forming a red mud phase and a clarified liquor phase; and

recovering the clarified liquor phase.

DESCRIPTION OF THE INVENTION

The present invention is directed to a process for forming substantiallydry water insoluble polymers from poly alkyl esters of vinylic monomers.The polymers are in the form of either homopolymers, copolymers orterpolymers. Preferably, the dried emulsion polymers are high molecularweight polymers of poly(methyl acrylate), poly(methyl acrylate/acrylicacid), poly(vinyl acetate/acrylic acid/methyl acrylate), poly(t-butylmethacrylate/acrylic acid/methyl acrylate) and poly(t-butylacrylate/acrylic acid/methyl acrylate).

The substantially dry polymers are not soluble in water but are solublein a caustic solution such as that found in the Bayer process.Typically, once hydrolyzed in the Bayer process liquors the driedpolymer has an intrinsic viscosity in 2N NaNO₃ at 30° C. of at least 15dL/g. Dried polymers formed from primarily acrylic acid esters andacrylic acid are not effective flocculating agents in the Bayer processas themselves. It is only after the polymers are hydrolyzed that theybecome effective as flocculants. The high alkalinity and hightemperatures of the Bayer process hydrolyze the esters over time to formpolymer acrylic acid or active sodium polyacrylate.

The hydrophobic nature of the dried polymers greatly increases theirease of storage, a moisture free environment is not necessary. Systemplugging and loss of product due to hydration are all but eliminated.The polymers are hydrolyzed primarily under high temperatures in acaustic environment. Additionally, the polymers can be added directly tothe process. Pre-hydrolyzation of the substantially dry polymers is notrequired but can be advantageous before using the polymers as aflocculant for the clarification of red mud containing liquors. Givensufficient residence time within the Bayer process system, hydrolyzationof the polymers will typically occur under the high temperature andcaustic environment of the Bayer process. When such a residence time isnot available the polymers can be added, at least in a portion, afterpre-hydrolyzation. Thus, the dry polymers may be added directly into theliquors as flocculants without the need for further processing.Additionally, the polymers do not substantially add to the organic loadof the system. Additionally, the substantially dry polymers may be addedhydrolyzed, in whole or in part. The polymers can be pre-hydrolyzedusing any compatible caustic solution for hydrolysis, but are typicallyhydrolyzed as a make-up solution using either the spent liquor, washeroverflow liquor, the return liquor from the mud lakes of the Bayerprocess or a combination thereof. The polymers are usuallypre-hydrolyzed when the residence time of the dried polymer would beinsufficient for the optimum amount of hydrolysis to occur, such as whenthe polymer is added to the washer stream. Furthermore, a combination ofdried polymer and pre-hydrolyzed polymer may be used. A portion of drypolymer may be added to the flash tanks or some other up-stream pointfrom the primary thickener and then a portion of pre-hydrolyzed polymeris added just before or into the center well of the thickener orclarification vessel.

The starting material for the substantially dry polymers is an aqueousemulsion polymer dispersion, which may be dried by any means known inthe art. The aqueous emulsion polymers are more fully described in U.S.Pat. No. 6,036,869, U.S. application Ser. No. 09/074,706 now U.S. Pat.No. 6,048,463 and U.S. application Ser. No. 09/203,314 now U.S. Pat. No.6,086,771, wherein the disclosures of which are hereby incorporated byreference.

In one embodiment, the aqueous dispersion of a high molecular weightwater-continuous emulsion polymer is dried using gas suspension dryingsuch as spray, flash and fluid-bed drying as well as hybrid systems.More preferably the emulsion is dried using a spray drier typicallyconsisting of spraying the emulsion into a gas stream through means suchas rotary atomizers, pressure nozzles, pneumatic nozzles and sonicnozzles. Spray drying normally begins with the atomization of the liquidfeed into fine droplets which are then contacted with a heated gasstream in which the droplets are suspended. The heated gas evaporatesthe liquid, leaving a substantially dry powder similar in size to thedroplets from which it was formed. The dried powder is then separatedfrom the gas and collected. The powder can be collected by cyclones,fabric filters or directly from the bottom of the chamber drying cone.

Important parameters in the spray drying process include; the gas outlettemperature, gas inlet temperature, and residence time. All threefactors are interrelated.

Residence time is calculated to be the volume of the dryer divided bythe volumetric gas flow. Typically, the residency time lasts no longerthan 1 minute, and is unlikely to ever exceed 2 minutes. Preferably, theresidency time is the longest practicable time for the dryer size used.It was observed that longer residency times produced a dryer finalproduct, which is preferred within reason. Thus, a residency time ofabout 45 seconds or above is preferred but an adequate dry polymer canbe obtained with a residency time as low as 10 seconds. Of courseoptimal residency times are affected by such parameters as the size andtype of spray dryer used and the efficiency at which it is operated andparameters such as inlet and outlet gas temperatures.

Gas outlet temperatures are preferably between 40° C. and 90° C., andmore preferably between 60° C. and 70° C. Any temperature is acceptableso long as adequate drying occurs. The outlet temperature is theresultant mix of the inlet temperature and the temperature of thepolymer injected into the gas stream, thus it is considerably lower intemperature than the gas inlet air. Generally, the gas outlettemperature will be the lowest possible temperature capable of giving adesired end product to reduce costs.

The gas inlet temperature is primarily regulated by what is practicaland economical. Additionally, the melting point of the polymer being fedmay be considered when determining an inlet temperature, since aresulting outlet temperature which exceeds the melting point of thepolymer may cause an unacceptable gel to form, resulting in a glass-likefinished product instead of the desired powdered product.

Moisture levels of the collected dried polymer particles are typicallyless than 5% by weight, and preferably less than 3% by weight. Of coursethe ultimate objective is to obtain a dried polymer with the lowestlevel of moisture possible. Dried polymers having a moisture levelgreater than 5% can be produced, but as moisture levels increase thechance for creating a gelled product increases.

In an alternative embodiment, the aqueous dispersion of high molecularweight water-continuous emulsion polymer is dried to form a filmcomprised of the dried aqueous dispersion substantially free of water,which is then ground to produce a powder of substantially dry polymerparticles. The emulsion polymer can be dried by any means capable ofdeveloping a film of dried polymer that can be ground.

Preferably, the emulsion can be dried by heating the emulsion in asuitable container or by spin-drying the emulsion. When heating theemulsion, temperatures can be as low as ambient temperatures and as highas up to 90° C. Once dried, the emulsion forms a film that can be groundinto a powder comprised of dried polymer particles. The film is groundto provide increased surface area to aid in the hydrolyzation of thepolymers under the high temperature caustic environment of the Bayerprocess. Preferably, the film is ground into particles having a diameterof less than 4 mm, but any size convenient for the administration of thedried polymer can be used. The ground dried polymer can be addeddirectly to the Bayer process slurry as a flocculant or after it ispre-hydrolyzed in a caustic solution.

The dry polymers produced by the processes described above are added toBayer process liquors containing dissolved sodium aluminate and red mudto aid in the recovery of alumina. The liquors to be treated include;the primary settler slurry which contains high levels of both red mudand dissolved sodium aluminate, red mud washing slurries and thesecondary clarification liquors. Additional liquors to be treatedinclude; red mud slurries which are dewatered in centrifuges or onvacuum drum or disc filters, as well as red mud slurries which areflocculated to improve their mud stacking properties or to improve thetendency to release water from the mud slurry.

The flocculation of the red mud by the dried polymers is mostchallenging in the primary clarification stage because of the highconcentration of fine particles and high total alkalinity. The polymersare able to reduce the solids found in the secondary clarificationstages by reducing the level of suspended solids that remain in thesupernatant above the floc formed in the primary settler liquor.

The Bayer process digests bauxite ore under highly alkaline conditionswhich can hydrolyze the dry polymers. Typically, the primary settlerliquors contain sodium or calcium hydroxide, sodium aluminate, andsodium carbonate. The total alkalinity of the primary settler istypically from about 100 to about 300 grams per liter of settler feed,as sodium carbonate. The solid content varies from about 25 to about 85grams per liter of settler feed.

The present dry polymers can be used for clarification and settling ofred mud-containing liquors in the Bayer process. Polymer additions canbe made to the red mud dewatered in either centrifuges or by vacuumfiltration (drum filters, and disc filters among others). Additionally,the polymers can be added to the red mud which is flocculated after thelast mud washing stage to improve the mud stacking properties in the muddisposal area.

Upon flocculation and settling of the primary settler feed by the drypolymers, a liquor/mud interface forms with a supernatant liquor low insuspended solids (generally ranging from about 10 to about 500 mg/l )overlying a mud layer. The lower mud layer of flocculated material iscomprised of both red mud solids (generally ranging from about 10% to70% mud solids by weight) and pregnant liquor. The overlying supernatantis a semi-clear liquor that is separated for secondary clarification.This supernatant is “mud-clear” and the interface between it and the mudlayer is clearly seen in some cases, but the supernatant is not entirelyfree of suspended solids, appearing instead as a hazy, but transparentliquid. The dry polymers diminish the amount of suspended solids in thesupernatant to decrease the extent of secondary clarification requiredto obtain the resulting sodium aluminate solution. Dry polymer additionmay also reduce or eliminate the need for added starch by providingimproved supernatant liquor clarity and improved red mud stability.

High alkalinity and elevated temperatures aid in hydrolyzing thesubstantially dry polymers. The intrinsic viscosity of the resultinghydrolyzed polymers are measured in 2N NaNO₃ at 30° C. and were fromabout 20 to 40 dL/g. The total alkalinity of the red mud containingliquor is from about 10 to 300 grams per liter expressed as sodiumcarbonate. The solids content of the red mud containing liquor is fromabout 10 grams per liter to 350 grams per liter. The treatment of thered mud containing liquor is typically conducted at atmospheric pressurebetween about 5° C. to 200° C. Preferably, the treatment of the red mudcontaining liquor can be conducted at atmospheric pressure and attemperatures between about 30° C. to 115° C. The treatment of theprimary settler feed is typically conducted at atmospheric pressures andat elevated temperatures from about 80° C. or 90° C. to about 103° C. or115° C.

The substantially dry polymers are preferably added upstream from theprimary settler in one of the flash tanks or between the flash tanks andthe primary settler feed well to provide sufficient temperature andresidence times for the hydrolysis of the polymer. It should be notedthat hydrolysis is not instantaneous. Hydrolysis typically progresses asthe polymer and mud make their way through the flash tanks and down thevarious piping into the primary settler. Additionally, the substantiallydry polymers can be added into the primary settler feed or directly intothe digesters.

Surprisingly, it has been discovered that through the formation ofmicro-floccules of the polymer and the suspended solids, a red mud isproduced which is more amendable to the bulk flocculation in the primarysettler. The micro-floccules form as the polymers hydrolyze and becomeactive toward the red mud, thus the polymers are preferably addedupstream of the primary settler.

The pre-hydrolyzed dry polymers may also be utilized to clarify thesuspended solids in any of the clarification vessels, e.g. settlers andwashers. Preferably, the polymers can treat any stage of the washerunderflow at the mud disposal site to improve mud stacking. Moreover,the polymers can be used in mud filters, including but not limited todrum and vacuum filters.

The substantially dry polymers may also be used in the following areasof the Bayer process including classification, flocculation,precipitation and dewatering of alumina trihydrate. Preferably, thepolymers can be used to flocculate and settle the alumina trihydrateBayer process product after the pregnant liquor is cooled. Furthermore,the substantially dry polymers can be used the Bayer process in theprecipitation and dewatering of solid phase oxalate.

The polymers from which the substantially dry polymers are formed may beeither a homopolymer, copolymer, or terpolymer. The chosen emulsionpolymers preferably have a high molecular weight, typically greater than3.0×10⁶. The polymer emulsions contain a surfactant and an emulsifierwhich can aid in the drying process. The emulsion polymers are describedin more detail as follows.

The copolymer emulsion can have a mole ratio of methyl acrylate toacrylic acid of from about 90:10 to about 99.5:0.5. The copolymerpreferably has a mole ratio of methyl acrylate to acrylic acid of97.5:2.5 to 99:1. The copolymers which are formed from acrylic acid andacrylic acid esters, include alkyl esters made from acrylic andmethacrylic acid and alcohols having from 1 to about 10 carbons. Thealkyl ester can have a straight or branched chain, and may containaliphatic and/or aromatic groups. The ester can be a methyl ester.

Polymer emulsions formed from acrylic acid and acrylic acid estermonomers ranging in composition from essentially 99% mer units of theacrylic acid ester monomer down to less than 50% mer units of acrylicacid ester monomer are used. Preferably, the molecular weights rangefrom about 4 million to 10 million. The high molecular weight of thepolymers produces upon hydrolysis a reduced specific viscosity (RSV) inthe range of from 30 up to 60 dl/g.

The surfactant added to the emulsion may be selected from the groupconsisting of sodium dodecyl benzene sulfonate, C₁-C₁₀ linear andbranched alkyl phenol ethoxylates, ethylene-oxide/propylene oxide blockcopolymers, sodium lauryl sulfate, ammonium sulfate salt of C₁-C₁₀linear or branched alkyl phenol ethoxylates, sodium sulfate salt ofC₁-C₁₀ linear or branched alkylphenol and combinations thereof. Thesurfactant may also be a combination of ammonium nonylphenol ethoxylatesulfate, octylphenol ethoxylate and ethylene oxide/propylene oxide blockcopolymer. Surfactants are typically in a ratio of from 55:15:30 to85:6:9 of ammonium sulfate salt of nonylphenol ethoxylate, octylphenolethoxylate and ethylene oxide/propylene oxide block copolymer.Preferably, the surfactants are in a relative ratio to one another of79:9:12 of ammonium sulfate salt of nonylphenol ethoxylate, octylphenolethoxylate and thylene oxide/propylene oxide block copolymer.

The initiators may be selected from the group consisting of redox pairsof transition metal ions/peroxides and inorganic reductants/oxidants.Preferably, the initiators may be potassium chlorate and ferrous sulfateheptahydrate. The monomers may be selected from the group consisting of(meth)acrylic acid, vinyl acetate, methyl acrylate, methyl methacrylate,nonyl-2-benzyl ester of acrylic acid, t-butyl acrylate, t-butylmethacrylate and combinations thereof.

The polymer emulsions are water continuous where the polymers aredispersed in water (true emulsions), with the water as the continuousphase, whereas conventional latex polymers are dispersed in an oil phasewith an inversion step being required before the polymers can be used asflocculants.

Polymers can be synthesized from other acrylic esters, conjugateddiolefins, monovinyl substituted aromatic compounds, methyl acrylate,methyl methacrylate, vinyl acetate, t-butyl acrylate, t-butylmethacrylate and other poorly water soluble vinylic compounds whichwould constitute the major component of the polymers. Any water solublevinylic monomer can be copolymerized with the above monomers, so long asthe level of the latter is significantly low, <10M %. Additionally,hydrophilic monomers such as sodium styrene sulfonate and sodium vinylsulfonate can be readily copolymerized with the above hydrophobicmonomers.

Most any emulsifier known in the art may be used in creating the driedpolymer emulsions. Example emulsifiers include: anionic, cationic andnonionic varieties of emulsifiers. Preferably, the emulsifiers are usedas a combination of anionic and nonionic emulsifiers. Linear andbranched alcohol sulfates, sodium (branched and linear) docecylbenzenesulfonate, sodium alpha olefin sulfonates, sulfated alkylphenolethoxylates, sulfated linear and branched alcohol ethoxylates,quaternary ammonium salts, fatty acid salts and ethoxylates of aliphaticand aromatic phosphate esters are among the preferred anionicsurfactants. Preferred nonionic emulsifiers are linear and branchedalcohol ethoxylates, alkylphenol ethoxylates, ethylene oxide-propyleneoxide (EP-PO) block copolymers and EO-PO block copolymers modified withethylenediamine. Preferred cationic emulsifiers are fatty amineethoxylates, fatty amine oxides, quaternary ammonium salts oxazoline andimidazoline based emulsifiers.

Various permutations of the emulsifiers at 2-15% based on the monomercan be utilized to obtain a shear stable system wherein little or no gelis obtained. Other requirements for the emulsifier combination includeminimum foaming during the deoxygenation with N₂ purge, extended shelfstability and easy dispersion into water. Foaming problems can beavoided by the utilization of a silicone based antifoam at 0.1-1.0%based on the product. Emulsion stability can be enhanced by the additionof polymeric stabilizers such as methyl cellulose, poly(vinyl alcohol),poly(vinyl pyrrolidone) and poly(ethylene glycol) which can be used inconjunction with the above emulsifiers.

In the above polymerization, the monomer concentration ranged from20-50%, more often at 30-40%. To overcome the gel problem,polymerization was conducted as a semi-batch process by adding themonomer(s) in 2-4 batches to the heel containing the emulsifier solutionin the reactor. To maximize the M_(w), the redox initiators were used atppm levels (1-15 ppm) and were fed continuously at a reactiontemperature of 5-15° C. A cessation of the exotherm was indicative ofthe monomer consumption. Thereafter, the reaction temperature was raisedto 25-35° C. and additional initiators were fed to reduce the residualmonomer level to less than 1%.

To control the molecular weight and to minimize long chain branching andimprove the polymer linearity, chain transfer agents such as alkylmercaptans, glycollic acid, thioglycollic acid, isopropanol and formicacid were used in the monomer phase, at 10 ppm to 10% based on themonomer.

Redox initiators were used to achieve a high M_(w) through lowtemperature polymerization. Redox initiator pairs include lower valencytransition metal ions such as Fe⁺², Cr⁺², V⁺², Ti⁺³, Co⁺², Cu⁺¹ andhydrogen peroxide or another hydroperoxide such as t-butyl or cumenehydroperoxide. Additional applicable initiator types include2-mercaptoethanol, thioglycollic acid or thiourea oxidized by Fe⁺³,Ce⁺⁴, bromate or persulfate ions. Moreover, combinations of inorganicreductants and oxidants such as persulfate/thiosulfate, chlorate/ferroussalt and persulfate/ferrous salt can produce radicals to initiate thepolymerization.

The following examples are provided to better illustrate the emulsionpolymers of the invention and are not meant to limit the inventionunless otherwise stated in the appended claims.

Dried Polymer

A substantially dry polymer according to an embodiment described in thepresent application was prepared on a pilot scale Tamato-Ohkawara DL-41Spray Drier at air temperatures between 100-200° C. and an air flow rateof 0.45-0.7 m³/min. The aspiration rate was held constant at 1.4 kg/cm².Using the synthesized polymer having a 99/1 mole percentwater-continuous formula produced better powder solids than thatproduced by the 94/6 mole percent formula. This difference is thought tobe due to the differing surfactant packages for the two formulas or to asmaller fraction of AA in the polymers. Additionally, it was discoveredthat as the drying residence times increased for a sample, the drier thepowder formed.

In Table I, the data resulting from testing two water-continuousemulsion polymers having different mole fractions is given. In the firstcolumn, the two polymers are listed in both the dry form and theemulsion form. Column two shows the percent polymer actives expressed asacrylic acid for each tested polymer. Column three lists the moisturedata. Columns four and five list the reduced specific viscosity for eachtested polymer after a specific hydrolysis period. The specificviscosity of the hydrolyzed polymers was measured in 2N NaNO₃ at 30° C.in column six, the replacement ratio vs. 100 mole % poly-amoniumacrylate benchmark flocculant is listed. The replacement ratio is howmuch of one polymer is needed to achieve the same results of anotherpolymer. The results indicate that the dry polymers gave essentiallyidentical performance as the emulsion polymer from which they arederived.

TABLE I p.AA RR_((actives)) Actives, Moisture RSV,dL/g RSV,dL/g vs. 100mole P.MA/AA % % (20 min) (45 min) % p.NH₄AA 94/6 mole % 15.7 — 41.034.0 0.7 emulsion 94/6 mole % 76.0 0.3-1.0 38.1 0.7 Dry powder 99/1 mole% 15.3 — 47.2 41.0 0.6 emulsion 99/1 mole % 63.5 0.5-1.5 42.2 38.6 0.6Dry powder

A substantially dry polymer was prepared according to an alternativeembodiment described in the present application by evaporating themoisture from the emulsion to form a film that is latter ground to apowder consisting of the substantially dry water insoluble polymers.

In Table II, the data resulting from an experiment of two samples ofground air-dried polymers is represented. In the experimentapproximately 60 grams of a Water-Continuous 98DF063 emulsion wasallowed to air dry overnight in a 6″ petri-dish to form a plastic film.For air-dried sample 1, the formed film was cut up with a pair ofscissors and the pieces were dissolved in a caustic solution. For sample2, the formed film was cut into large approximately 1″ square pieces andthen ground through a Brinkman (Retsch) rotating screen grinder. Thepowder was then dissolved in a caustic solution.

As noted from the experiment, there was some loss in polymer RSV upongrinding, the unground air-dried sample 1 having an RSV of 36 dL/g andthe ground air-dried sample 2 having an RSV of 29 dL/g. Both drypolymers have p.MA/AA chemistries which are converted to predominatelypoly acrylate p.NaAA/AA after hydrolysis in the caustic solution. Bothsamples gave similar settling performance, with the dosage responsecurve for sample 2 having a curve that is not as steep as that forsample I consistent with sample 2 having a lower RSV.

TABLE II Product Mud Overflow Dosage Dosage Settling Clarity g product/Polymer Rate 10 min. Flocculant ton mud solids, ppm ft/hr NTU Air-DriedSample 1 85 3.6 3 315 Air-Dried Sample 1 128 5.3 21 392 Air-Dried Sample1 156 6.5 49 420 Air-Dried/Ground Sam- 88 3.6 2 219 ple 2Air-Dried/Ground Sam- 110 4.5 11 345 ple 2 Air-Dried/Ground Sam- 132 5.319 343 ple 2 Air-Dried/Ground Sam- 165 6.7 25 382 ple 2 98DF063 293 3.89 214 98DF063 379 5.1 24 380 98DF063 450 6.1 33 391 Laboratory PreparedSlurry with 42.2 g/L Red Mud Solids (actual plant spent liquor andJamaican Bauxite)

Homopolymer

An oil in water emulsion of poly(methyl acrylate) homopolymer wassynthesized in the following manner. In a 1 liter polymerization flaskfitted with baffles, 561.49 g of deionized water, 54.3 g of nonylphenolethoxylate sulfate ammonium salt (58% solution), available fromRhone-Poulenc of Cranbury, N.J., 4.9 g of octylphenol ethoxylate (70%),available from Rhone-Poulenc of Cranbury, N.J., 4.8 g of EO-PO blockcopolymer available from BASF, Mt. Olive, N.J., 0.1 g EDTA tetra sodiumsalt and sulfuric acid (0.02 g) were taken and a solution was effectedby mixing. To the clear solution, 5.0 g of Sag 2001, an antifoam agentavailable from Witco of Greenwich, Conn. was added, and nitrogen wasthen sparged through the solution for 15 minutes, after which thesolution was cooled to 10° C.

The monomer, methyl acrylate (99%—353.54 g), and formic acid (0.175 g)were mixed in an addition funnel. A third of the monomer was added tothe emulsifier solution in the reactor and nitrogen sparge was continuedfor additional 10 minutes. Ferrous heptahydrate (0.002 g) was dissolvedin sulfuric acid (0.07 g) solution in water (6.9 g) and the potassiumchlorate (0.0019 g) was dissolved in water (6.9 g). The initiatorsolutions were drawn into separate syringes and fitted into meteredsyringe pumps. The initiators were pumped in at a slow rate to maintaina constant reaction temperature (10-13° C.). When an exotherm was nolonger perceptible, the initiator addition was stopped and another thirdof the monomer was added to the reactor. Polymerization was repeated asdescribed above. Finally, the third lot of the monomer was added tocomplete the polymerization.

After completing the polymerization, the reaction temperature was raisedto 25° C. to reduce the unreacted monomer to a level bellow 2%. Thepolymer was collected to determine the gel No. (100 mesh screen) andhydrolyzed for 1 hr at 85° C. in caustic at 1% emulsion concentration todetermine the residual monomer by liquid chromatography (for acrylicacid) and the reduced specific viscosity, intrinsic viscosity, andmolecular weight. The hydrolyzed MA homopolymer has an RSV of 28.3 dL/gand the polymer has a molecular weight of between 4.4×10⁶ and 5.2×10⁶.

Copolymer

The following is an example of the preparation of a high molecularweight copolymer. The copolymer formed is poly(methyl acrylate/acrylicacid) having a 94/6 mole ratio.

In a 1 liter polymerization flask fitted with baffles was addeddeionized water (552.9 g), nonylphenol ethoxylate sulfate ammonium salt(19.84 g of 58% solution), available from Rhone-Poulenc of Cranbury,N.J., sodium dodecyl benzene sulfonate (17.44 g of 23% solution)available from the same, and EO-PO block copolymer (3.88 g) availablefrom BASF, Mt. Olive, N.J. and EDTA tetra sodium salt (0.96 g ) weretaken and a solution was effected by mixing. To the resultant clearsolution was added SAG 2001 (0.19 g), an antifoaming agent availablefrom Witco of Greenwich, Conn. and then nitrogen was sparged through thesolution for 15 minutes with the solution being cooled down to 10° C.

Methyl acrylate (99%) 367.2 g, AA 19.19 g, and formic acid (0.15 g) weremixed in an addition funnel. A third of this mixture was added to theemulsifier solution in the reactor and the nitrogen sparge was continuedfor additional 10 minutes. Ferrous sulfate heptahydrate (0.002 g) wasdissolved with sulfuric acid (0.07 g) and water (9.65 g) and then thepotassium chlorate (0.0019 g) was dissolved in water (6.9 g). Theinitiator solutions were drawn into separate syringes and fitted intometered syringe pumps.

The initiators were pumped in at a slow rate to maintain a constantreaction temperature of 10-13° C. When an exotherm was no longerperceptible, the initiator addition was stopped and another third of themonomer was added to the reactor. Polymerization was repeated asdescribed above. Finally, the third lot of the monomer was addedcompleting the polymerization. After polymerization the reactiontemperature was raised to 25° C. and held for approximately an hour toreduce the unreacted monomer level to below 2 percent.

Terpolymer

The following illustrates the preparation of a terpolymer. A 19:6:75mole ratio poly(vinyl acetate/acrylic acid/methylacrylate) wassynthesized in the following manner. In a 1 liter polymerization flaskfitted with baffles, 295.0 g of deionized water, 10.34 of nonylphenolethoxylate sulfate ammonium salt (58% solution), available fromRhone-Poulenc of Cranbury, N.J., 9.02 g of sodium dodecyl benzenesulfonate (23% solution) available from the same, and 2.0 g of EO-POblock copolymer available from BASF, Mt. Olive, N.J. were taken and asolution was effected by mixing. To the resultant clear solution 0.1 9 gof SAG 2001, an antifoam agent available from Witco of Greenwich, Conn.and vinyl acetate (99%) 40.8 g were added, nitrogen was sparged throughthe solution for 15 minutes and the solution was cooled down to 10° C.

Methyl acrylate 99% (151.1 g—AA 10.0 g) and glycolic acid (0.2 g) weremixed in an addition funnel. A third of this mixture was added to theemulsifier solution in the reactor and the nitrogen sparge was continuedfor additional 10 minutes.

Ferrous sulfate heptahydrate (0.003 5 g) was dissolved with sulfuricacid (0.1 g) solution in water (9.65 g) and the potassium chlorate(0.0032 g) were dissolved in water (0.68 g). The initiator solutionswere drawn into separate syringes and fitted into metered syringe pumps.

The initiators were pumped in at a slow rate to maintain a constantreaction temperature of 10-13° C. When an exotherm was no longerperceptible, the initiator addition was stopped and another third of themonomer was added to the reactor. Polymerization was repeated asdescribed above. Finally, the third lot of the monomer was added andpolymerization was completed. After polymerization the reactiontemperature was raised to 25° C. and held for approximately an hour toreduce the unreacted monomer level to below 2 percent.

Changes can be made in the composition, operation and arrangement of themethod of the present invention described within, without departing fromthe concept and scope of the invention as defined in the followingclaims.

What is claimed is:
 1. A process for producing substantially dry waterinsoluble high molecular weight polymers from poly alkyl esters ofvinylic monomers comprising: spray-drying into a gas stream an aqueousdispersion of a high molecular weight water-continuous emulsion polymerincluding, an emulsifier, a surfactant, and water, and, having anintrinsic viscosity in 2N NaNO₃ at 30° C. of at least 15 dL/g; andcollecting the resultant polymer particles.
 2. The process of claim 1,further including a residence time of about 15 seconds to about 120seconds.
 3. The process of claim 1, wherein the substantially drypolymer has a residual moisture level of less than 3% by weight.
 4. Theprocess of claim 1, wherein the gas outlet temperature is between about40 and about 100° C.
 5. The process of claim 1, wherein the aqueousdispersion of a high molecular weight water-continuous emulsion polymeris comprised of a homopolymer formed from the free radicalpolymerization of monomer.
 6. The process of claim 1, wherein theaqueous dispersion of a high molecular weight water-continuous emulsionpolymer is comprised of a terpolymer formed from the free radicalpolymerization of monomers.
 7. The process of claim 1, wherein theaqueous dispersion of a high molecular weight water-continuous emulsionpolymer is comprised of a copolymer formed from the free radicalpolymerization of monomers.
 8. The process of claim 1, wherein thedispersion further includes the emulsion polymer selected from the groupconsisting of: an emulsion copolymer formed from free radicalpolymerization monomers methyl acrylate and acrylic acid and wherein thecopolymer has an intrinsic viscosity in 2N NaNO₃ at 30° C. of at least18 dL/g; an emulsion homopolymer of methyl acrylate having an intrinsicviscosity in 2N NaNO3 at 30° C. of at least 15 dl/g, an emulsionterpolymer, and a combination of a high molecular weight emulsioncopolymer formed from monomers methyl acrylate and acrylic acid havingintrinsic viscosity in 2N NaNO₃ at 30° C. of from at least 19 dL/g witha lower molecular weight emulsion copolymer formed from monomers methylacrylate and acrylic acid having intrinsic viscosity in 2N NaNO₃ at 30°C. of from about 5 to about 18 dL/g to improve a filtration rate of theslurries.
 9. The process of claim 8, wherein the terpolymer is formedfrom free radical polymerization of monomers selected from the groupconsisting of methyl acrylate, methyl methacrylate, t-butyl acrylate,t-butyl methacrylate, acrylic acid and vinyl acetate.
 10. The process ofclaim 8, wherein the terpolymer is represented by the formula ofp.MA/AA/X, wherein MA is selected from the group consisting of methylacrylate and methyl methacrylate, AA is acrylic acid and X is selectedfrom the group consisting of t-butyl acrylate, t-butyl methacrylate andvinyl acetate.
 11. The process of claim 10, wherein the terpolymer has amole ratio of 1-20% t-butyl acrylate or t-butyl methacrylate, 0.5-10%acrylic acid and 70%-98.5% methyl acrylate or methyl methacrylate. 12.The process of claim 10, wherein the terpolymer has a mole ratio of1-20% vinyl acetate, 0.5-10% acrylic acid and 70%-98.5% methyl acrylateor methyl methacrylate.
 13. The process of claim 8, wherein thecopolymer has mole ratio of methyl acrylate to acrylic acid of fromabout 90:10 to about 99.5:0.5.
 14. The process of claim 10, wherein thecopolymer has a mole ratio of methyl acrylate to acrylic acid of fromabout 85:15 to about 99.9:0.1.
 15. The process of claim 10, wherein thecopolymer has an intrinsic viscosity in 2N NaNO₃ at 30° C. from about 20to about 40 dL/g.
 16. A process for producing substantially dry waterinsoluble high molecular weight polymers from poly alkyl esters ofvinylic monomers comprising: drying an aqueous dispersion of a highmolecular weight water-continuous emulsion polymer including anemulsifier, a surfactant and water and having an intrinsic viscosity in2N NaNO₃ at 30° C. of at least 15 dL/g; forming a film comprised of thedried aqueous dispersion substantially free of water; and grinding thefilm to form a powder of substantially dry polymer particles.
 17. Theprocess of claim 16, wherein the dry polymer particles having a diameterof no greater than 4 mm.
 18. The process of claim 16, wherein the powderhas a residual moisture level of less than 3% by weight.
 19. The processof claim 16, wherein the drying of the aqueous dispersion occurs at atemperature between about 30° C. and about 90° C.
 20. The process ofclaim 16, wherein the step of drying of the aqueous dispersion furtherincludes spin drying the dispersion.